Copper nanoparticle-embellished Zr-based metal-organic framework for electrocatalytic hydrogen evolution reaction.

Copper nanoparticles (Cu NPs) have gained immense popularity in catalysis by virtue of their impressive properties and earth abundance. Herein, we incorporated small-sized copper nanoparticles into the amine-functionalized NU-1000 MOF and used this composite material as an effective catalyst for electrocatalytic Hydrogen Evolution Reaction (HER) studies.

Immobilization of Gold Nanoparticles on Postsynthetically Modified NU-1000 for Hydrogen Evolution Reaction.

NU-1000, being a hydrothermally stable metal-organic framework (MOF), with structural robustness is viable for functionalization with various entities. A postsynthetic modification strategy called solvent-assisted ligand incorporation (SALI) is chosen for functionalizing NU-1000 with thiol moieties using 2-mercaptobenzoic acid. In accordance with soft acid-soft base interactions, the thiol groups on NU-1000, as a scaffold, can immobilize the gold nanoparticles without much aggregation. The catalytically active gold sites on thiolated NU-1000 are utilized for hydrogen evolution reaction (HER). The catalyst delivered an overpotential of 101 mV at a current density of 10 mAcm-2 in 0.5 M H2SO4. The faster charge transfer kinetics determined from the Tafel slope of 44 mV/dec enhances the HER activity. The sustainable performance of the catalyst for 36 h proves its utility as a potential catalyst to produce neat hydrogen.

Catalytically active silver nanoparticles stabilized on a thiol-functionalized metal-organic framework for an efficient hydrogen evolution reaction.

A post-synthetic technique, Solvent Assisted Ligand Incorporation (SALI), was used for thiol functionalization in the zirconium-based metal-organic framework NU-1000. This thiol-functionalized MOF was employed as a support for the growth of silver nanoparticles (Ag NPs) through coordination of a Ag(I) complex with a node-anchored thiol-ligand, followed by the reduction of Ag(I) to Ag(0). X-ray photoelectron spectroscopy revealed that the ratio of Ag(0) to Ag(I) proportionally increased with the loading of silver ions. The HER activity increased with the enhancement of Ag(0) in the system and the best efficiency was observed for the composite with ∼95% Ag(0). This composite displayed an overpotential of 165 mV in an acidic medium at 10 mA cm-2 and a Tafel slope of 53 mA dec-1. The loading of silver beyond the optimum value led to the aggregation of the particles which affected the overpotential substantially. The catalyst demonstrated appreciable static stability for 24 h, which promotes the use of the material as an HER catalyst. Therefore, these results emphasized that Ag NPs embedded onto a thiol-functionalized MOF is a propitious material for developing a clean and renewable energy source.

Silver Nanoparticle-Incorporated Defect-Engineered Zr-based Metal-Organic Framework for Efficient Multicomponent Catalytic Reactions.

Small-sized silver nanoparticles are incorporated into a thiol-functionalized stable Zr-based metal-organic framework (MOF). Thiol functionalization has been carried out using 2-mercapto benzoic acid (2-MBA) as the modulator, which promotes defect formation in the MOF structure. The incorporation of silver nanoparticles aided by the silver-sulfur interactions in this defective MOF gives rise to catalytic activity. Its catalytic efficiency in the highly atom-efficient A3 coupling reaction has been studied for a variety of substrates with impressive recyclability. The synergistic effect of the electron-rich silver core and electron-deficient surface of the thiol-bonded silver nanoparticle is key for this catalytic reaction.